Catalytic apparatus



Nov. 21, 19336 K. RoKA 1,936,118

CATALYTIC APPARATUS Fil ed Nov. 11, 1929 2 Sheets- Sheet 2 IN VEN TOR.'

A TTORNEYS.

Nov. 21, 1933. ROKA 1,936,118

CATALYTIC APPARATUS Filed NOV; 11, 1929 2 Sheets-Sheet l INVENTOR.KBo/ia A TTORNEYS.

UNITED STATES PATENT o1=1=1c1-:

In carrying out catalytic gas CATALYTIC Koloman Roka,

mesne assignments, Gold- 11ml Silber- APPARATUS Konstanz, Germany,assignor, by

to the firm Deutsche Scheideanstalt vormals Roessler,Frankfort-on-the-Main, Germany, a corporation of Germany ApplicationNovember 11, 1929, Serial No. 406,437,

and in 5 Claims.

reactions which take place with the addition or evolution of heat careis taken to lead the vapour mixtures through 5 catalyst, cooledexternally or heated by hot gases.

cross section and consequently gases or the gas and pipes packed withthe for example by air the capability of such catalyst pipe to allow thegases to pass are placed within extremely narrow the fact that withincreasing limits owing to diameter of the pipes the exchange of heatbetween the separate portions of the catalyst material and the outerwall becomes increasingly less effective. It is, therefore, necessary,

when working with large amounts of gas, to employ a correspondinglylarge number of pipes individually of relatively small diameter,

but connected up in-parallel.

It has been found that catalytic gas reactions, in particular suchreactions as require an I exact maintenance of a particularly highdegree, or which owing to specially temperatures to such reactions greatabsorption or definite evolution of 'heat require a specially energeticaction of the cooling or heating means,

can be carried out considerably better and with greater certainty inreaction vessels that their inner space surfaces parallel with of such afiat shape is mainly bounded by two one another or substantiallyparallel, the distance between which is small relatively to the otherdimensions of the container so that the distance of the catalyst fromthe container wall does not exceed at any place the limits within whicha sufficiently rapid heat exchange is possible, with the result that thecontainers so obtained, for example of pocket shape, are moreover S0formed that the catalyst may be easily introduced and removed, and atthe same time a good ing gas over the whole lyst is ensured.

distribution of the entercross section of the cata- With suchcontainers, on accountv of the large containing space of which mayamount to the individual containers,

about 100 litres, the furcontrast with sets that the catalyst can befilled into the containers and removed from the same very much morequickly owing to the smaller number of filling and emptying'openings andthat furthermore any small irregularities in the thickness of thefilling are very easily compensated over the whole cross section ofpipes the resistance is never the same in with the result that thecontainer while with a set of to the passage of the gases each of theseparate pipes,

the gases in such cases The increase in the.

Germany November 28, 1928 will flow through the pipes of lowerresistance in larger amounts than through those with greater resistance.Consequently for example in lower temperature limits permissible forthereaction.

The same is the case in the converse direction with endothermicreactions in which the desired reaction temperatures must be produced byuniform supply of external heat.

These drawbacks naturally are the more serious in proportion to thenarrowness of the temperature limits for the gas reactions to be carriedout or to the amounts of heat to be supplied or withdrawn, the resultbeing that on the one hand not only incomplete conversion takes place inthe cold pipes, and on the other hand the formation of decompositionproducts in the parts of the cata--' lysts which are too hot, but alsothe catalyst is injured by overheating.

By employing containers according to the invention the said drawbacksare largely avoided, and owing to the uniform flow of the gasesthroughthese containers it is possible to use them in larger numbersconnected in parallel, because the relative differences in the capacityof the individual containers to allow the flow of gas becomes muchsmaller than between the individual small units when pipes are used.

A further advantage in contrast with such pipes is the avoidance ofnumerous connecting members, and of the corresponding number of pointsat which there are packed joints which easily give rise to losses ofgas.

The described method of working has proved to be of particular advantagein the production of ketones, especially acetone from acetylene,alcohols, esters, aldehydes or other bodies capable of forming ketonesby the treatment of these bodies with steam at high temperatures, forexample temperatures between 250 and 650 C., in the presence of suitablecatalysts, especially oxygen light metals in the presence or absence ofmetals, which latter when present preferably serve as the carrier forthe oxygen compounds of metals, preferably in intimate contacttherewith.

It has been found that in an oven assembly with pocket shaped reactionvessels for example constructed in the manner described hereinafter, allthese reactions, whether they take place exothermically, endothermicallyor without substantially sensible heat effects, may be carried out in aparticularly favorable manner and with a substantially decreased ovenspace and correspondingly simplified oven construction as contrastedwith a set of pipes.

It is also possible without further steps to use one and the same ovenassembly for example for the endothermic formation of ketones fromalcohol, and also for the exothermic formation of ketones fromacetylene.

The production of hydrogen from water gas as well as hydrogenation anddehydrogenation proc advantage in assemblies of reaction vessels of thekind described. The production of hydrogen takes place according to theequation:

CO+HzO. H2+CO2 10 kilocalories.

In order to have as complete as possible a conversion it is, asis known,important to keep the reaction temperature as low as possible, since itis only at low temperatures that the balance lies sufiiciently on thehydrogen side. This again requires the use of specially activecatalysts, that is to say, catalysts which make possible a sufficientspeed of reaction at low temperatures, and these again are sensitive inregard to high temperatures which may occur temporarily if the heat ofreaction is insufiiciently led away. The sharp temperature regulationnecessarily following from these considerations is easily made possiblewhen carrying out the reaction according to the present invention.

While in the production of hydrogen the evolution of heat is not initself too great and is partly taken up also by the steam which ispresent in excess, this is not the case in hydrogenation processes inwhich about 20 kilocalories are set free per molecule of the hydrogenobtained. On the other hand, in these reactions, the catalysts employed(such as nickel or copper reduced with special precautions, and onsuitable carriers) are very specially sensitive to overheating so thatif the heat is not removed sufliciently rapidly these catalysts becomevery quickly inactive.

It is known for example that for these reasons it is difiicult tohydrogenate acetaldehyde on a technical scale to form ethyl alcohol.This state of affairs is still more marked for example in the productionof butyl alcohol from croton aldehyde in which for each molecule ofbutyl alcohol two molecules of hydrogen must be formed with the releaseof about 40 kilocalories. It has been found that these reactions alsocan be carried out with great advantage in pocket shaped reactionvessels according to the invention.

It has been found further that in carrying out such catalytic gasreactions,for example the above ed production of ketones, the preheatingand prepurification of the gases, vapours or gasvapours mixtures to besupplied to the reaction vessels, may be carried out with good-resultsin same kind, for example the preheating may be carried out in a veryuniform and well controlled manner in such vessels which a filled with amaterial of good heat conductivity and sufficient heat capacity, as forexample scrap iron or other metallic bodies. Similarly, gases or vapoursor gas-vapour mixtures from which tarry or other materials injurious tothe catalyst may separate out at the commencement of heating,

may be purified by passing them through pocket shaped containersaccording to the invention which are packed for example with coke oranother suitable filling material, before passing them through the mainreaction vessels.

In this case also the purification occurs specially easily andthoroughly in consequence of the cooperation of the good temperatureregulation and the uniform subdivision of the gas currents both over thecross section of the individual reaction vessels and over a plurality ofsuch vessels connected in parallel.

A number of, embodiments of reaction vessels suitable for use incarrying out the method of working describedare illustrated in theannexed drawings wherein:

Figure l is an elevation of such a vessel from the side.

Figure 2 the same on Figure 3 is a cross of Figure 1, and

Figure 4 is a perspective view of a number of such vessels connected inparallel.

In these drawings 1 and 2 indicate the parallel side walls which boundthe greater part of the inner space of the container, and which arespaced a small distance apart relatively to the other dimensions of thevessel, which is provided on its outer surface wholly or partly withribs 3 or similar members. 4 and 5 are end tubes for filling in andremoving the catalyst or other filling material and for supplying andtaking off gases, they are preferably located between the side walls 1and 2 at opposite ends of the container so that the change in crosssection of the vessel from that of the tubes 4, 5, conveniently of thesame diameter as the relative distance apart of the walls 1 and 2, iseffected by the oblique surfaces 6 to 9.

These tubes are conveniently provided with lateral subsidiary flangedopenings 10 and 11 which for example serve for supplying and taking offthe gas and by means of which also a number of such containers may beconnected in common to connecting pipes in the case of the parallelconnection shown in Figure 4. The vessels in some instances may be builtwithout ribs. Tubes 4 and 5 not employed for connecting purposes, butonly for filling or emptying purposes could be closed in anysuitablemanner for example as is shown in Figure 1 in connection with the tube 4by means of a clamp closure 12 together with a cover 13 or in any othermanner.

The filling and the removal of the catalyst or other filling bodies issubstantially facilitated by the uniform narrowing of the cross sectionof the vessel for example by the inclined end walls 6 to 9 towards theinlet and outlet openings, and, moreover, a uniform distribution isensured for inlet and outlet over the whole crosssection of the vessel.The union tubes mounted at the ends of the vessel preferably have adiameter which is equal to the distance between the main boundary walls1 and 2 of the vessel. One of the openings of the vessel, for examplethe upper opening, serves for filling in the catalyst and the other forremoving the same. This takes place very easily and quickly, includingany parthe line A-B of Figure 1, while section on the line C-D is acentral longitudinal section of p. 3

faces 1 and 2 of the reaction vessel must not exceed ratio between thewidth and length of paratus of For example, the

stead of being made fiat as showncould be made internally with ribs,ticlesadhering to are preferably selected the walls of the vessel,since these can be easily moved from the filling unions and all theseoperations are also easily carried out with the vessels built into thefurnace.

The clear distance between-the two main sur- 200 millimeters in general.The width of the vessel is limited by the necessity of being able todistribute the catalyst from the filling opening over the whole crosssection of the vessel. The width will generally lie between 500 and 1000millimeters. The height ofthe pocket shaped unit depends upon'thedetails of the reaction to be .carried out. If it is carried outconveniently in relatively thin layers of catalyst the pocket shapedreaction vessel is relatively short. on the other hand if it is aquestion for example of a reaction which proceeds slowly and whichrequires a large volumeof catalyst, long pockets In a similar fashionthe the pocket the existing special working millimeters and more.

is always adapted to conditions. a

The vessels according to the invention are with advantage provided ontheir outer surface with ribs, as shown at 3 in the drawings, whichincrease the surface of the pocket giving out or absorbing heat withrespect to the heating or cooling medium, for example warm or coldgases, as well as conducting these gases in the desired paths. v

The preliminary treatment of the gases in apthis kind has essentialworking advantages because the control of a unit comprising apparatus ofthe same construction is much simpler and a preheating of the reactiongases is simultaneously attained with the preliminary treatment. Theshape of the reaction vessels may naturally be varied within wide limitswithout departing from the scope of the present invention.

main boundary walls 1', 21nof other shapes, for example of wave shapewhilst still being a substantially constant distance apart, and ifdesired could be provided arranged in any suitable mannerwhatever, orround on its narrow sides and so forth.

' In a similar way the reduction of cross-section of the vessel from themain part to the ends where according to the drawings the filling andemptying tubes are mounted, instead of being effected by obliquesurfaces, could be effected by any other suitable guiding surfaceswhatever. Also instead of providinga tube at each end of the vessel twoor more of such at one or both ends, and, moreover tubes may be providedat other parts of the vessel, for exofi the reaction gases, for examplein such a way that the supply of the reaction gases may take placethrough a tube mounted half way along the vessel; for example in.

the middle of one of surfaces from one or both sides of oil at the theboundary the vessel, and the gases may betaken ends of the vessel orconversely.

According to the invention a large number of such vessels may beconnected in series with one another as well as in parallel. Theparallel connection, as shown in w l, may be conveniently effected, forex p ,"by' connecting the lateral auxiliary unions 0 the, necessarynumbers of vessels at one and the same end to a corup to a length of2000 the vessel may be made tubes may be mounted of introducing andleading responding number of tubes provided on cross pipes, so that uponpassing from one set of vessels to the next connected behind it, onlyone connecting bend, or in the case number of pockets two, arenecessary.

The'advantages of the above-described method of connecting together aseries of vessels in parallel by means of cross connections arisesparticularly in the above described method of" work-- ing if the gasesare passed, before their introduc vessel properpacked with tion into thereaction catalyst, through vessels of the same kind packed with suitablefilling bodies with the object, for example, of preheating or separatinginjurious constituents, since for connecting the parallel series ofvessels only one or at the most two pipes are necessary, so that withoutusing a large number of pipe connections the perature afforded by thefurnaceutilized in the manner heating can be form of connection.

The connection ofthe vessels in series is preferably arranged so thatthe reaction gases in the first vessel for example are allowed to fiowfrom the top towards the bottomin the-second, from the bottom towardsthe top and so the result that the length of the necessary pipeconnections is very much reduced. As a result it is not necessary toconnect the vessels in the series sequence according to their positionin space, but they maybe connected in another furnace heatl heat and thelike, and thus frequently a devious flow of the gases, in whichindividual vessels or groups of vessels are passed over, proves to bepreferable. By assembling together pockets connected in parallel, it ispossible with the help of cross pipes to connect together in any desiredseries sequence with a mi mum amount of connecting pipes the vessels ofthe assemblies increased by the parallel connection.

In order to produce a particularly uniform temperature or a particularlyconveniently graded temperature distribution, this particular method ofconnection, for example that in which the gas passes first from thefirst parallel connec'ted series of pockets into the last i. e. thethird and then only passes to the middle series, may be found ofimportance.

If for examplethe case of an endothermic reof a very large mostfavorable for car-., rying out the process by employing the desiredforth, with temperature and amounts of distribution of temaction occursas is illustrated by the production I of acetone from alcohol, wherein,moreover, in consequence of the excess of water vapour fairly largeamounts of heat are necessary for the preheating, the method ofconnection may for example with-great advantage in certain cases be suchthat the vapour mixture is first led into the pre-heating pockets whichlie the furnace in which the heating gases are already relativelycooled, and in fact preferably in counter-current to the heating gases,that is to say in such a way that the vapour mixture first passes intothe last or coolest pocket, then into the one before that and so on.When in this way the vapour mixture is raised to the temperature atwhich the reaction commences, the mixture'is led into the foremost ofthe pockets packed "with the catalyst proper on which-the heating gasfirst strikes. In this pocket the greaterpart of'the conversion isconsequently completed. In order to maintain the reaction temperaturethe most vigorous supply of heat is required from this foremost pocket.Then the mixture, already in that part of converted for the greaterpart, flows into the second and third pockets now in counter-currentwith the heating gases corresponding to the smaller heat requirementsfor completion of the 5 conversion. If the pockets according to theirseries sequence in the furnace gases are indicated as 1, 2, 3, 4,

5 and 6 in cases of the kind referred to, the

sequence of connection 6, 5, 4, 1, 2, 3, or a simi- 10 lar sequencewould be advantageous. Obviously a heat exchanger for exchanging heatbetween the gas or vapour mixture to be supplied and that flowing awaymay be provided outside the furnace assembly proper or the heatrelations may be regulated in the desired fashion in any other desiredmanner.

In the case for example of exothermic reactions the connection will bemade quite differently according to the amount of heat released duringthe reaction and according to the insulation of the furnace.- The mostsuitable method of. connection can, however, in each case be foretoldwith a certain probability, and the success ,is easily confirmed by theresult of tests.

I claim:-

1. A reaction apparatus for ca rying out catalytic reaction with organicgaseous compounds, comprising a plurality of reaction-chambers beingsubstantially filled withpowdery or lumpy catalysts or other fillingmaterial and having two of their walls substantially parallel to eachother and forming between them an elongated zone of a cross section inwhich the thickness is small relative to the width, said reactionchambers having cylindrical portions at each end, the internal diametersof which are substantially the same as the thickness of said zone andtapered portions situated respectively between the body portion and theadjacent cylindrical portion, 40- said reaction-chambers being disposedwith the aforesaid walls of adjacent chambers in register with, spacedapart from and substantially parallel to one another. a 2. A reactionapparatus for carrying out catalytic reaction with organic gaseouscompounds,

comprising a plurality of reaction-chambers being substantially filledwith powdery or lumpy catalysts or other filling material and having twoof their walls substantially parallel to each other and forming betweenthem an elongated zone of a cross section in which the thickness issmall relative to the width, said reaction-chambers being disposed withthe aforesaid walls of adjacent chambers in'register with, spaced apartfrom and substantially parallel to one another, and said walls havringprojecting ribs on their external surfaces.

3. A reaction apparatus for carrying out catalytic reaction with organicgaseous compounds. comprising a plurality of reaction-chambers beingsubstantially filled with powdery or lumpy catalysts or other fillingmaterial and having two of their, walls substantially parallel to eachother and forming between them an elongated zone of a cross section inwhich the thickness is small relative to the width, saidreaction-chambers being disposed with the aforesaid walls of adjacentchambers in register with, spaced apart from and substantially parallelto one another, and said walls having on their external surfacesprojecting ribs extending perpendicularly to the length of thereaction-chambers.

4. A reaction apparatus for carrying out catalytic reaction with organicgaseous compounds, comprising a plurality of reaction-chambers beingsubstantially filledlwith powdery or lumpy catalysts or other fillingmaterial and having two of their walls substantially parallel to eachother and forming between them an elongated zone of a cross section inwhich the thickness is small relative to the width, saidreaction-chambers being disposed with the aforesaid walls of adjacentchambers in register with, spaced apart from and substantially parallelto one another, and said walls having on their external surfacesprojecting ribs extending perpendicularly to the length of thereaction-chambers, the ribs on each wall cooperating with the ribs on,the wall opposed thereto to provide flue-passages therebetween.

5. A reaction apparatus for carrying out catalytic reaction with organicgaseous compounds, comprising a plurality of reaction-chambers beingsubstantially filled with powdery or lumpy 15 catalysts or other fillingmaterial and having two of their walls substantially parallel to eachother and forming between them an elongated zone of a cross section inwhich the thickness is small relative to the width, saidreaction-chambers being disposed side-by-side, with their aforesaidwalls substantiallyparallel and provided with projecting ribs, an inletpipe, an outlet pipe, and

pipe connections connecting the openings at one end oi thereaction-chambers in common to the inlet pipe and the opening at theother end in common to the outlet pipe.

KOLOMAN ROKA.

